CN108624236B - SiCp/Al composite material grinding and polishing liquid and preparation method thereof - Google Patents
SiCp/Al composite material grinding and polishing liquid and preparation method thereof Download PDFInfo
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- CN108624236B CN108624236B CN201810646122.6A CN201810646122A CN108624236B CN 108624236 B CN108624236 B CN 108624236B CN 201810646122 A CN201810646122 A CN 201810646122A CN 108624236 B CN108624236 B CN 108624236B
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- 238000005498 polishing Methods 0.000 title claims abstract description 79
- 239000007788 liquid Substances 0.000 title claims abstract description 35
- 238000000227 grinding Methods 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 19
- 239000010432 diamond Substances 0.000 claims abstract description 19
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 16
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 14
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005642 Oleic acid Substances 0.000 claims abstract description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 7
- 239000000194 fatty acid Substances 0.000 claims abstract description 7
- 229930195729 fatty acid Natural products 0.000 claims abstract description 7
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 7
- 229920000767 polyaniline Polymers 0.000 claims abstract description 7
- 239000010705 motor oil Substances 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 239000003755 preservative agent Substances 0.000 claims description 3
- 230000002335 preservative effect Effects 0.000 claims description 3
- 239000010721 machine oil Substances 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 12
- 238000003754 machining Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 3
- 239000010699 lard oil Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000006061 abrasive grain Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000004439 roughness measurement Methods 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Grinding-Machine Dressing And Accessory Apparatuses (AREA)
Abstract
The invention discloses a SiCp/Al composite material grinding and polishing liquid and a preparation method thereof, belonging to the field of precise and ultra-precise grinding and polishing of special difficult-to-machine materials. Due to the particularity of the aluminum-based silicon carbide composite material, the common polishing solution cannot meet the requirement of a special polishing solution developed for precision machining. The polishing solution comprises the following components: diamond micropowder with the particle size of 0.5-2.5 microns, 40% of engine oil, 20% of methyl silicone oil, 8% of sodium hydroxide, 5% of oleic acid, 5% of span, 3% of polyaniline, 0.5% of water-soluble organic silicon oxidized alkane, 0.5% of chlorinated fatty acid and 18% of deionized water. The aluminum-based silicon carbide workpiece processed by the lapping and polishing liquid has the advantages of uniform surface quality, basically no scratch, high processing efficiency, greenness, no pollution, reduced subsurface damage, small friction coefficient and stable processed surface quality.
Description
Technical Field
The invention belongs to the technical field of precise and ultra-precise grinding and polishing, and mainly aims at grinding and polishing liquid developed for similar superhard and difficult-to-process materials such as SiCp/Al composite materials and the like. The polishing solution can be widely applied to the fields of precision instruments such as aviation, aerospace, automobiles and the like.
Background
Compared with the traditional single material, the SiCp/Al composite material is different from the traditional single material, is a SiC particle reinforcement with low density, high strength and high elastic modulus is added into a relatively soft metal aluminum matrix, so that the SiCp/Al composite material has a series of advantages of wear resistance, small thermal expansion coefficient, stable size and the like, has become the best substitute material of aluminum alloy, partial titanium alloy and the like, and is known as a third-generation aerospace inertia device material, but because the SiC particle reinforcement is completely different from the Al alloy matrix, the processing is more difficult than the simple metal or nonmetal difficult-to-process material, the processed surface defect is extremely serious, the workpiece is more difficult to process along with the increase of the volume fraction and the particle size of the SiC particle reinforcement phase, the exertion and the wide application of the excellent performance are seriously restricted, and the domestic composite material mainly aims at the low volume fraction with the SiC particle content of about 20 percent, the method is characterized in that the precise polishing is carried out by adopting the polishing liquid on the basis of ELID grinding, a series of complex phenomena such as chemical reaction and the like occur under the auxiliary action of pressure and chemical processing liquid during grinding, so that the removal rate of the material is improved, and a deteriorated layer is reduced and completely eliminated.
Disclosure of Invention
The invention aims to solve the problem that the conventional method cannot process the SiC-based SiC composite material and cannot meet the requirements of practical application because the Al alloy is easy to be burnt and adhered to the surface of a workpiece due to the superhard characteristic of SiC in the SiCp/Al, the conventional composite material which is difficult to process by grinding and polishing the SiCp/Al is processed by common grinding paste, so that defects are easily generated and have grinding and polishing grains, the surface of the Al alloy is difficult to remove, the damage influence of the defect of brittle fracture of SiC particles on the integrity of the grinding surface is great, and the mirror grinding and polishing effect is difficult to achieve. The SiCp/Al polishing liquid is easy to polish and does not generate polishing lines in the polishing process, so that the surface of a SiCp/Al workpiece can achieve the mirror surface polishing effect. When the polishing pad is used, the prepared polishing liquid is only needed to be added on the polishing pad, and a workpiece is placed for processing, so that the polishing pad is convenient to operate, high in efficiency, low in cost and free of pollution.
The technical scheme adopted by the invention is SiCp/Al composite material grinding and polishing liquid, which is characterized in that: diamond micropowder, 40% of engine oil, 20% of silicone oil, 8% of sodium hydroxide, 5% of oleic acid, 5% of span, 3% of polyaniline, 0.5% of water-soluble organic silicon oxidized alkane, 0.5% of chlorinated fatty acid and 18% of deionized water.
The particle size of the diamond micro powder is 0.5-2.5 μm.
The preparation method of the SiCp/Al composite material polishing solution comprises the following specific steps:
adding diamond micro powder with the particle size of 0.5-2.5 microns into methyl silicone oil, wherein the mass ratio of the diamond micro powder to the methyl silicone oil is 3:4, heating the methyl silicone oil to about 50 ℃, and then starting stirring to obtain a mixed solution of the diamond micro powder and the methyl silicone oil which are uniformly stirred and mixed;
secondly, adding engine oil into the uniformly stirred and mixed diamond micro powder and methyl silicone oil mixed solution, heating to 60-70 ℃, adding a sodium hydroxide aqueous solution while stirring, heating to 100-110 ℃, carrying out heat preservation reaction for 3-5 hours, stopping heating, and cooling to room temperature for later use;
thirdly, under the condition of stirring, adding 5 percent of nonionic surfactant span, 3 percent of preservative polyaniline, 0.5 percent of chlorinated fatty acid, 0.5 percent of water-soluble organic siloxane defoaming agent, 18 percent of deionized water and 5 percent of oleic acid into the mixed solution which is cooled to room temperature for later use, continuously stirring, and stopping stirring after the solution is uniformly stirred to obtain the SiCp/Al composite material grinding and polishing solution.
The SiCp/Al polishing liquid related by the invention is different from the traditional polishing liquid, and has the main advantages that:
the grinding and polishing liquid is different from the traditional grinding and polishing liquid, mainly aims at the processing of superhard materials, does not need to add grinding materials during processing, and can be directly used;
the sodium hydroxide is added into the SiCp/Al polishing liquid, and the sodium hydroxide, the Al and the SiC can generate a series of chemical reactions, so that a workpiece is dissolved in the polishing liquid, the polishing belongs to chemical mechanical polishing, the material removal rate is improved, the surface quality of the SiCp/Al is improved, and meanwhile, the generated sodium metasilicate can be used as a corrosion inhibitor to inhibit a corrosion process together with a nonionic surfactant span, so that the reaction is carried out towards a direction favorable for polishing;
(3) the machined surface is easy to form a physical adsorption lubricating film, the friction can be reduced, the cooling performance is good, no pollution is caused, and the quality stability of the machined surface is high;
drawings
FIG. 1 is a graph showing the effect of a polishing liquid on SiCp/Al processing.
FIG. 2 is a diagram showing the processing effect of a common oil engine polishing liquid on SiCp/Al.
FIG. 3 is a graph showing the effect of a conventional water-based polishing liquid on SiCp/Al processing.
FIG. 4 is a graph showing the results of polishing liquid roughness measurements.
FIG. 5 is a graph of results of measuring roughness of the lapping liquid in the oil machine.
FIG. 6 is a graph showing the roughness measurement of the water-based polishing liquid.
FIG. 7 is a polishing fluid processing topography.
FIG. 8 is a machining topography of the lapping liquid of the oil machine.
FIG. 9 is a water-based polishing fluid processing profile.
Detailed Description
A high-volume-fraction aluminum-based silicon carbide composite material grinding and polishing experiment is designed, and the advantages of the grinding and polishing liquid are highlighted by comparing the influence of the grinding and polishing liquid and common grinding and polishing liquid on the surface processing quality of the SiCp/Al composite material.
1. Lapping and polishing liquid experiment
First implementation condition
Experimental equipment: BDE-1B frequency-conversion speed-regulation optical two-axis grinding and polishing machine, surface roughness measuring instrument TR300, S-3400N II type scanning electron microscope;
grinding and polishing conditions: the environment temperature is room temperature, SiCp/Al polishing liquid, an aluminum-based silicon carbide composite material processing workpiece and a velvet polishing pad are adopted;
the polishing parameters are as follows: the rotation speed of the polishing disk is 150-300 rpm, and the polishing pressure is 0.2-0.4 KN/cm2The polishing eccentricity is 20mm, the frequency is 16-20Hz, and the polishing time is 30-60 min.
Preparation of the polishing liquid
According to the volume ratio: 40% of engine oil, 20% of methyl silicone oil, 8% of sodium hydroxide, 5% of oleic acid, 5% of span, 3% of polyaniline, 0.5% of water-soluble organic silicon oxidized alkane, 0.5% of chlorinated fatty acid and 18% of deionized water.
The preparation method of the polishing solution comprises the following specific steps:
firstly, mixing 0.5-2.5 mu m diamond micro powder according to the weight ratio of 3:4 adding methyl silicone oil, heating to about 50 ℃, and starting stirring;
secondly, after stirring and mixing uniformly, adding engine oil into the first step, heating to 60-70 ℃, adding an aqueous solution of sodium hydroxide under the stirring condition, heating to 100-110 ℃, keeping the temperature for reaction for 3-5 hours, stopping heating, and cooling to room temperature for later use;
sequentially adding a nonionic surfactant span, a preservative polyaniline, chlorinated fatty acid and a water-soluble organic siloxane defoaming agent under the stirring condition, adding the rest water and oleic acid, continuously stirring, and stopping stirring after the solution is uniformly stirred to obtain the aluminum-based silicon carbide polishing solution.
2. Comparative experiment A
Experimental example 1 for implementation conditions
Slurry for common oil machine
The preparation ratio of the polishing solution is as follows: after a diamond abrasive (the diameter of abrasive particles is 1-1.5 mu m) with the granularity of W1 and industrial lard oil are uniformly stirred and mixed, 60 percent of kerosene and 10 percent of industrial lard oil are added according to the volume ratio, and then 2 percent of boric acid, 1 percent of emulsified silicone oil and 17 percent of water are added.
The preparation method comprises the following steps:
adding diamond abrasive (the diameter of abrasive grains is 1-1.5 mu m) with the granularity of W1 into melted lard oil according to the volume ratio of 3:4, and stirring uniformly.
And secondly, adding 60 percent of kerosene into the mixed solution according to the volume ratio, heating to 60-80 ℃, and stirring until the kerosene is completely dissolved.
Thirdly, pouring the boric acid, the emulsified silicone oil and the water into a clean container and stirring the mixture evenly.
Fourthly, the solution obtained from the second step and the solution obtained from the third step are mixed and stirred evenly, and the temperature is reduced to the room temperature.
Comparative experiment B
Experimental example 1 for implementation conditions
Grinding and polishing liquid for common water-based machine
The preparation ratio of the polishing solution is as follows: the diamond abrasive with the granularity of W1 (the diameter of the abrasive grain is 1-1.5 mu m) is added with 3 percent of benzotriazole, 5 percent of sodium molybdate, 2 percent of organosilicon, 0.5 percent of acrylate and 89.5 percent of water according to the volume ratio.
The preparation method comprises the following steps:
firstly, adding benzotriazole, sodium molybdate, organic silicon, acrylate and the rest water into a diamond abrasive (the diameter of abrasive particles is 1-1.5 mu m) with the granularity of W1 in sequence, heating to 40-50 ℃, and uniformly stirring until the materials are completely dissolved.
And (3) grinding and polishing result analysis: as can be seen from table 1 and the accompanying drawings, under the same process conditions, namely: the rotation speed of the polishing disk is 250rpm, and the polishing pressure is 0.4KN/cm2When the polishing eccentricity is 20mm, the frequency is 16Hz, and the polishing time is 60min, the three polishing liquids are adopted to respectively carry out the polishing experiment on SiCp/Al, and the following results can be found: by using polishing liquidThe surface of the workpiece basically has no scratch, the surface quality is greatly improved, and as can be seen from figures 8 and 9, SiC particles are pulled out to form holes on the surface, Al matrix is smeared to cause obvious burn, surface cracks are expanded to further cause the surface of the workpiece to be torn, and more surface defects exist, so that the comparison shows that the grinding and polishing effect of the grinding and polishing liquid is superior to that of the common grinding and polishing liquid, the effect is obvious, the surface quality is uniform, and the processing surface precision is high.
TABLE 1 surface roughness after polishing
Claims (3)
- The SiCp/Al composite material polishing liquid is characterized by comprising the following components in parts by weight: diamond micropowder, according to the volume ratio: 40% engine oil, 20% methyl silicone oil, 8% sodium hydroxide, 5% oleic acid, 5% span, 3% polyaniline, 0.5% water-soluble organic silicon oxidized alkane, 0.5% chlorinated fatty acid and 18% deionized water; the mass ratio of the diamond micro powder to the methyl silicone oil is 3: 4.
- 2. the SiCp/Al composite material grinding and polishing liquid as claimed in claim 1, wherein the particle size of the diamond micro powder is 0.5 ~ 2.5.5 μm.
- 3. The SiCp/Al composite polishing fluid as set forth in claim 1, wherein: the preparation method of the SiCp/Al composite material polishing solution comprises the following specific steps:adding diamond micro powder with the particle size of 0.5 ~ 2.5.5 mu m into methyl silicone oil, wherein the mass ratio of the diamond micro powder to the methyl silicone oil is 3:4, heating the methyl silicone oil to 50 ℃, and then starting stirring to obtain a uniformly stirred and mixed solution of the diamond micro powder and the methyl silicone oil;adding machine oil into the uniformly stirred and mixed diamond micro powder and methyl silicone oil mixed solution, heating to 60 ~ 70 ℃, adding a sodium hydroxide aqueous solution while stirring, heating to 100 ~ 110 ℃, keeping the temperature for reaction for 3-5 hours, stopping heating, and cooling to room temperature for later use;sequentially adding a nonionic surfactant span, a preservative polyaniline, chlorinated fatty acid and a water-soluble organic siloxane defoaming agent under the stirring condition, adding the rest water and oleic acid, continuously stirring, and stopping stirring after the solution is uniformly stirred to obtain the aluminum-based silicon carbide polishing solution.
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| CN102250581A (en) * | 2011-04-14 | 2011-11-23 | 阜新天源钢球制造有限公司 | Circulating hard grinding agent of diamond micro powder grinding fluid as well as preparation and use methods thereof |
| CN104911011A (en) * | 2015-06-29 | 2015-09-16 | 北京工业大学 | ELID (Electrolytic In-process Dressing)-based high-volume-fraction aluminum-based silicon carbide composite grinding fluid and preparation method of grinding fluid |
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| CN102250581A (en) * | 2011-04-14 | 2011-11-23 | 阜新天源钢球制造有限公司 | Circulating hard grinding agent of diamond micro powder grinding fluid as well as preparation and use methods thereof |
| CN104911011A (en) * | 2015-06-29 | 2015-09-16 | 北京工业大学 | ELID (Electrolytic In-process Dressing)-based high-volume-fraction aluminum-based silicon carbide composite grinding fluid and preparation method of grinding fluid |
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Inventor after: Guan Jialiang Inventor after: Zhang Longyue Inventor after: Zhang Yu Inventor after: Hu Zhiyuan Inventor before: Guan Jialiang Inventor before: Zhang Yu Inventor before: Hu Zhiyuan Inventor before: Zhang Longyue |
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| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191220 |